Thermal silicon etch

ABSTRACT

Exemplary methods for selectively removing silicon (e.g. polysilicon) from a patterned substrate may include flowing a fluorine-containing precursor into a substrate processing chamber to form plasma effluents. The plasma effluents may remove silicon (e.g. polysilicon, amorphous silicon or single crystal silicon) at significantly higher etch rates compared to exposed silicon oxide, silicon nitride or other dielectrics on the substrate. The methods rely on the temperature of the substrate in combination with some conductivity of the surface to catalyze the etch reaction rather than relying on a gas phase source of energy such as a plasma.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 15/918,860, filed Mar. 12, 2018, and which is hereby incorporated by reference in its entirety for all purposes.

TECHNICAL FIELD

The present technology relates to semiconductor processes and equipment. More specifically, the present technology relates to selectively etching silicon.

BACKGROUND

Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a pattern in photoresist into underlying layers, thinning layers, or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process that etches one material faster than another facilitating, for example, a pattern transfer process. Such an etch process is said to be selective to the first material. As a result of the diversity of materials, circuits, and processes, etch processes have been developed with a selectivity towards a variety of materials.

Etch processes may be termed wet or dry based on the materials used in the process. A wet HF etch preferentially removes silicon oxide over other dielectrics and materials whereas a wet phosphoric acid etch preferentially removes silicon nitride. However, wet processes may have difficulty penetrating some constrained trenches and also may sometimes deform the remaining material. Dry etches produced in local plasmas formed within the substrate processing region can penetrate more constrained trenches and exhibit less deformation of delicate remaining structures. However, local plasmas may damage the substrate through the production of electric arcs as they discharge.

Thus, there is a need for improved systems and methods that can be used to produce high quality devices and structures. These and other needs are addressed by the present technology.

SUMMARY

Exemplary methods for etching silicon may include flowing a fluorine-containing precursor into a substrate processing region of a semiconductor processing chamber. A substrate may be positioned within the substrate processing region and the substrate may include silicon and dielectric. The silicon and the dielectric may be exposed on sidewalls of a trench formed in stacked alternating layers of the silicon and the dielectric. The methods may further include removing silicon from the sidewalls of the trench.

In some embodiments removing silicon from the sidewalls of the trench may include laterally etching silicon from the sidewalls of the trench. The dielectric may be one of silicon oxide or silicon nitride. The silicon may include one of amorphous silicon, single crystal silicon or polysilicon. The removal of the silicon may remove silicon with a horizontal etch progression. The removal of the silicon may remove silicon at an etch rate more than twenty times faster than dielectric. The removal of the silicon may be performed at a substrate temperature of less than 500° C. The removal of the silicon may be performed at a partial pressure of fluorine-containing precursor which is more than 1 Torr. The stacked alternating layers may include at least 50 layers of alternating layers of the silicon and the dielectric. The trench may have an aspect ratio of greater than or about 50:1. A layer of the silicon at an upper region of the trench and a layer of silicon at a lower region of the trench may differ in lateral etch amounts by less than about 2 nm. The fluorine-containing precursor may be one of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluoride, hydrogen fluoride, or xenon difluoride.

The present technology may also encompass additional etching methods. The additional etching methods may include flowing a fluorine-containing precursor into a substrate processing region of a semiconductor processing chamber. The substrate may be positioned within the substrate processing region and the substrate may include polysilicon and dielectric. The polysilicon and the dielectric may be exposed on sidewalls of a trench formed in stacked alternating layers of the polysilicon and the dielectric. The methods may further include laterally etching the polysilicon from the sidewalls of the trench.

In some embodiments the lateral removal of polysilicon may remove polysilicon with a horizontal etch progression. The lateral removal of polysilicon may remove polysilicon at an etch rate more than twenty times faster than the dielectric. The lateral removal of polysilicon may be performed at a temperature of less than 600° C. The lateral removal of polysilicon may be performed at a partial pressure of fluorine-containing precursor within the substrate processing region which is more than 1 Torr. The trench may possess an aspect ratio of greater than 50:1. The stacked alternating layers may include at least 50 layers of alternating layers of the polysilicon and the dielectric. A layer of the polysilicon at an upper region of the trench and a layer of silicon at a lower region of the trench may differ in lateral etch amounts by less than 2 nm.

Such technology may provide numerous benefits over conventional systems and techniques. For example, the processes may enable the patterning of integrated circuit features having reduced feature sizes. Additionally, the operations of some embodiments of the present technology may increase etch selectivity of crystalline silicon or amorphous silicon while retaining more exposed silicon nitride and/or silicon oxide. The etch selectivity of polysilicon relative to silicon oxide or silicon nitride may also be increased relative to conventional processes. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures.

DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the embodiments may be realized by reference to the remaining portions of the specification and the drawings.

FIG. 1 shows a top plan view of one embodiment of an exemplary processing system according to embodiments of the present technology.

FIG. 2A shows a schematic cross-sectional view of an exemplary processing chamber according to embodiments of the present technology.

FIG. 2B shows a detailed view of a portion of the processing chamber illustrated in FIG. 2A according to embodiments of the present technology.

FIG. 3 is a schematic diagram of a substrate processing chamber which can be used to carry out selective etch processes according to embodiments.

FIG. 4 shows exemplary operations in a method according to embodiments of the present technology.

FIG. 5 shows exemplary operations in a method according to embodiments of the present technology.

FIGS. 6A and 6B show cross-sectional views of substrates being processed according to embodiments of the present technology.

Several of the figures are included as schematics. It is to be understood that the figures are for illustrative purposes, and are not to be considered of scale unless specifically stated to be of scale. Additionally, as schematics, the figures are provided to aid comprehension and may not include all aspects or information compared to realistic representations, and may include superfluous or exaggerated material for illustrative purposes.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the letter.

DETAILED DESCRIPTION

In transitioning from 2D NAND to 3D NAND (also known as VNAND), many process operations are modified from vertical to horizontal operations because the levels are distributed vertically. Additionally, as 3D NAND structures grow in the number of cells being formed, the aspect ratios of memory holes and other structures increase, sometimes dramatically. During 3D NAND processing, stacks of vertically alternating placeholder layers and inter-electrode dielectric layers exist early in the device formation. These placeholder layers are then removed and replaced with polysilicon layers. While polysilicon may be incorporated on one side of the cell structure, operations may have previously been performed on the other side of the structure, such as forming floating gates or charge-trap layers. Several operations involve etching the placeholder layers or recessing the polysilicon layers. Manufacturing VNAND devices benefits from an even removal rate of etched layers across the vertical distribution of the layers.

Because of the high aspect ratios of VNAND structures, penetrating the entire length to access cells at the bottom of the hole may be difficult. Conventional dry etch techniques may have difficulty with adequate diffusion of precursors to the bottom of the memory hole. Accordingly, the etchants often begin etching the top cell layers before even reaching the bottom cell layers, which may not occur or may occur to only a limited degree. This may end up producing a V-shape through the either memory holes or slit trenches where substantial etching may have occurred at slabs or other features at or near the top of the memory hole. Perhaps minimal or sometimes no etching has been performed at or near the bottom of the memory holes or slit trenches. Conventional technologies sometimes use wet etches to access slabs or other repeated features to perform a lateral etch to recess or remove the features. However, wet etching may be more robust than other etching techniques, and the wet etching may etch the features further than necessary or desired especially in the case of forming recesses. For example, the wet etching may etch each layer significantly, and may detrimentally etch each layer almost through completely to other nearby memory holes. Excessive etching may make placing the cell layers in the appropriate or desired location more difficult, and may weaken the structures causing deformation. Additionally, as structures continue to shrink in size, the surface tension of fluids used in wet etching can cause pattern collapse or sticking issues.

The present technology overcomes these issues by performing a dry etch process that allows precursors to diffuse adequately through the cell materials before substantial etching has occurred at the upper regions of the cell. By introducing a fluorine-containing precursor in the absence of a plasma and maintaining a low substrate temperature, a surface-limited etching reaction of silicon (e.g. polysilicon or single crystal silicon) may be made exceedingly uniform despite large aspect ratio features such as slit trenches and memory holes found in VNAND devices. In embodiments, full diffusion through a slit trench or memory hole may occur to allow more uniform etching. Thus, a similar etching profile may be formed through polysilicon features at the top of the memory hole and the bottom of the memory hole. The present technology may allow uniformly sized cells to be produced throughout the vertical stack, unlike other dry etch techniques. Additionally, the entire process may be performed in a single chamber depending on the operations performed, unlike wet etch techniques that require transferring the processed substrate between multiple chambers to perform the wet etch and then dry the substrate. Additional process information will be described while and also after exemplary hardware is disclosed.

Although the remaining disclosure will routinely identify specific etching processes utilizing the disclosed technology, it will be readily understood that the systems and methods are equally applicable to deposition and cleaning processes as may occur in the described chambers. Accordingly, the technology should not be considered to be so limited as for use with etching processes or chambers alone. Moreover, although an exemplary chamber is described to provide foundation for the present technology, it is to be understood that the present technology can be applied to virtually any semiconductor processing chamber that may allow the single-chamber operations described.

FIG. 1 shows a top plan view of one embodiment of a substrate processing system 101 of deposition, etching, baking, and curing chambers according to embodiments. In the figure, a pair of front opening unified pods (FOUPs) 102 supply substrates of a variety of sizes that are received by robotic arms 104 and placed into a low pressure holding area 106 before being placed into one of the substrate processing chambers 108 a-f, positioned in tandem sections 109 a-c. A second robotic arm 110 may be used to transport the substrate wafers from the holding area 106 to the substrate processing chambers 108 a-f and back. Each substrate processing chamber 108 a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

The substrate processing chambers 108 a-f may include one or more system components for depositing, annealing, curing and/or etching a dielectric film on the substrate wafer. In one configuration, two pairs of the processing chambers, e.g., 108 c-d and 108 e-f, may be used to deposit dielectric material on the substrate, and the third pair of processing chambers, e.g., 108 a-b, may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers, e.g., 108 a-f, may be configured to etch a dielectric film on the substrate. Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments. It will be appreciated that additional configurations of deposition, etching, annealing, and curing chambers for dielectric films are contemplated by system 100.

FIG. 2A shows a cross-sectional view of an exemplary process chamber system 200 with partitioned plasma generation regions within the processing chamber. During film etching, e.g., silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, etc., a process gas may be flowed into the first plasma region 215 through a gas inlet assembly 205. A remote plasma system (RPS) 201 may optionally be included in the system, and may process a first gas which then travels through gas inlet assembly 205. The inlet assembly 205 may include two or more distinct gas supply channels where the second channel (not shown) may bypass the RPS 201, if included.

A cooling plate 203, faceplate 217, ion suppressor 223, showerhead 225, and a substrate support 265, having a substrate 255 disposed thereon, are shown and may each be included according to embodiments. The pedestal 265 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate, which may be operated to heat and/or cool the substrate or wafer during processing operations. The wafer support platter of the pedestal 265, which may comprise aluminum, ceramic, or a combination thereof, may also be resistively heated in order to achieve relatively high temperatures, such as from up to or about 100° C. to above or about 1100° C., using an embedded resistive heater element.

The faceplate 217 may be pyramidal, conical, or of another similar structure with a narrow top portion expanding to a wide bottom portion. The faceplate 217 may additionally be flat as shown and include a plurality of through-channels used to distribute process gases. Plasma generating gases and/or plasma excited species, depending on use of the RPS 201, may pass through a plurality of holes, shown in FIG. 2B, in faceplate 217 for a more uniform delivery into the first plasma region 215.

Exemplary configurations may include having the gas inlet assembly 205 open into a gas supply region 258 partitioned from the first plasma region 215 by faceplate 217 so that the gases/species flow through the holes in the faceplate 217 into the first plasma region 215. Structural and operational features may be selected to prevent significant backflow of plasma from the first plasma region 215 back into the supply region 258, gas inlet assembly 205, and fluid supply system 210. The faceplate 217, or a conductive top portion of the chamber, and showerhead 225 are shown with an insulating ring 220 located between the features, which allows an AC potential to be applied to the faceplate 217 relative to showerhead 225 and/or ion suppressor 223. The insulating ring 220 may be positioned between the faceplate 217 and the showerhead 225 and/or ion suppressor 223 enabling a capacitively coupled plasma (CCP) to be formed in the first plasma region. A baffle (not shown) may additionally be located in the first plasma region 215, or otherwise coupled with gas inlet assembly 205, to affect the flow of fluid into the region through gas inlet assembly 205.

The ion suppressor 223 may comprise a plate or other geometry that defines a plurality of apertures throughout the structure that are configured to suppress the migration of ionically-charged species out of the first plasma region 215 while allowing uncharged neutral or radical species to pass through the ion suppressor 223 into an activated gas delivery region between the suppressor and the showerhead. In embodiments, the ion suppressor 223 may comprise a perforated plate with a variety of aperture configurations. These uncharged species may include highly reactive species that are transported with less reactive carrier gas through the apertures. As noted above, the migration of ionic species through the holes may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through the ion suppressor 223 may advantageously provide increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn may increase control of the deposition and/or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity, e.g., SiNx:SiOx etch ratios, Si:SiOx etch ratios, etc. In alternative embodiments in which deposition is performed, it can also shift the balance of conformal-to-flowable style depositions for dielectric materials.

The plurality of apertures in the ion suppressor 223 may be configured to control the passage of the activated gas, i.e., the ionic, radical, and/or neutral species, through the ion suppressor 223. For example, the aspect ratio of the holes, or the hole diameter to length, and/or the geometry of the holes may be controlled so that the flow of ionically-charged species in the activated gas passing through the ion suppressor 223 is reduced. The holes in the ion suppressor 223 may include a tapered portion that faces the plasma excitation region 215, and a cylindrical portion that faces the showerhead 225. The cylindrical portion may be shaped and dimensioned to control the flow of ionic species passing to the showerhead 225. An adjustable electrical bias may also be applied to the ion suppressor 223 as an additional means to control the flow of ionic species through the suppressor.

The ion suppressor 223 may function to reduce or eliminate the amount of ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may still pass through the openings in the ion suppressor to react with the substrate. It should be noted that the complete elimination of ionically charged species in the reaction region surrounding the substrate may not be performed in embodiments. In certain instances, ionic species are intended to reach the substrate in order to perform the etch and/or deposition process. In these instances, the ion suppressor may help to control the concentration of ionic species in the reaction region at a level that assists the process.

Showerhead 225 in combination with ion suppressor 223 may allow a plasma present in first plasma region 215 to avoid directly exciting gases in substrate processing region 233, while still allowing excited species to travel from chamber plasma region 215 into substrate processing region 233. In this way, the chamber may be configured to prevent the plasma from contacting a substrate 255 being etched. This may advantageously protect a variety of intricate structures and films patterned on the substrate, which may be damaged, dislocated, or otherwise warped if directly contacted by a generated plasma. Additionally, when plasma is allowed to contact the substrate or approach the substrate level, the rate at which oxide species etch may increase. Accordingly, if an exposed region of material is oxide, this material may be further protected by maintaining the plasma remotely from the substrate.

The processing system may further include a power supply 240 electrically coupled with the processing chamber to provide electric power to the faceplate 217, ion suppressor 223, showerhead 225, and/or pedestal 265 to generate a plasma in the first plasma region 215 or processing region 233. The power supply may be configured to deliver an adjustable amount of power to the chamber depending on the process performed. Such a configuration may allow for a tunable plasma to be used in the processes being performed. Unlike a remote plasma unit, which is often presented with on or off functionality, a tunable plasma may be configured to deliver a specific amount of power to the plasma region 215. This in turn may allow development of particular plasma characteristics such that precursors may be dissociated in specific ways to enhance the etching profiles produced by these precursors.

A plasma may be ignited either in chamber plasma region 215 above showerhead 225 or substrate processing region 233 below showerhead 225. Plasma may be present in chamber plasma region 215 to produce the radical precursors from an inflow of, for example, a fluorine-containing precursor or other precursor. An AC voltage typically in the radio frequency (RF) range may be applied between the conductive top portion of the processing chamber, such as faceplate 217, and showerhead 225 and/or ion suppressor 223 to ignite a plasma in chamber plasma region 215 during deposition. An RF power supply may generate a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

FIG. 2B shows a detailed view 253 of the features affecting the processing gas distribution through faceplate 217. As shown in FIGS. 2A and 2B, faceplate 217, cooling plate 203, and gas inlet assembly 205 intersect to define a gas supply region 258 into which process gases may be delivered from gas inlet 205. The gases may fill the gas supply region 258 and flow to first plasma region 215 through apertures 259 in faceplate 217. The apertures 259 may be configured to direct flow in a substantially unidirectional manner such that process gases may flow into processing region 233, but may be partially or fully prevented from backflow into the gas supply region 258 after traversing the faceplate 217.

The gas distribution assemblies such as showerhead 225 for use in the processing chamber section 200 may be referred to as dual channel showerheads (DCSH) and are additionally detailed in the embodiments described in FIG. 3. The dual channel showerhead may provide for etching processes that allow for separation of etchants outside of the processing region 233 to provide limited interaction with chamber components and each other prior to being delivered into the processing region.

The showerhead 225 may comprise an upper plate 214 and a lower plate 216. The plates may be coupled with one another to define a volume 218 between the plates. The coupling of the plates may be so as to provide first fluid channels 219 through the upper and lower plates, and second fluid channels 221 through the lower plate 216. The formed channels may be configured to provide fluid access from the volume 218 through the lower plate 216 via second fluid channels 221 alone, and the first fluid channels 219 may be fluidly isolated from the volume 218 between the plates and the second fluid channels 221. The volume 218 may be fluidly accessible through a side of the gas distribution assembly 225.

FIG. 3 is a bottom view of a showerhead 325 for use with a processing chamber according to embodiments. Showerhead 325 may correspond with the showerhead 225 shown in FIG. 2A. Through-holes 365, which show a view of first fluid channels 219, may have a plurality of shapes and configurations in order to control and affect the flow of precursors through the showerhead 225. Small holes 375, which show a view of second fluid channels 221, may be distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 365, and may help to provide more even mixing of the precursors as they exit the showerhead than other configurations.

Using the chambers and hardware presented herein, no local plasma may be present according to embodiments. In addition, no remote excitation may be applied to the fluorine-containing precursors described herein in embodiments. As such, the substrate processing region and any remote plasma regions (if present and through which the fluorine-containing precursor passes) may be devoid of plasma or may be “plasma-free” as defined here. Absence (or reduction in magnitude) of plasma is desirable to make the present silicon etch processes more selective, delicate and isotropic. The term “plasma-free” will be used herein to describe the substrate processing region or any remote regions during application of no or essentially no plasma power to the regions. The etchants (the fluorine-containing precursor) described possess energetically favorable etch reaction pathways which enable the substrate processing region and any remote regions to be plasma-free during operations of etching silicon or polysilicon herein. Stated another way, the electron temperature in the substrate processing region and/or remote regions may be less than 0.5 eV, less than 0.45 eV, less than 0.4 eV, or less than 0.35 eV according to embodiments. Moreover, the fluorine-containing precursor may have not been excited in any remote plasma prior to entering the substrate processing region in embodiments. For example, if a remote plasma region or a separate chamber region is present and used to conduct the fluorine-containing precursor toward the substrate processing region, the separate chamber region or remote plasma region may be plasma-free as defined herein.

The chambers discussed previously may be used in performing exemplary methods including etching methods. FIG. 4 shows exemplary operations in a method 400 according to embodiments of the present technology. Prior to the first operation of the method a substrate may be processed in one or more ways before and during operation 405. A VNAND structure is formed on a patterned substrate during operation 405. For example, one or more memory holes or slit trenches may be formed through the stacked layers. The vertically distributed layers of the VNAND may include any number of materials, and may include alternating layers of a placeholder material and a dielectric material. In embodiments the dielectric material may be or include silicon oxide, and the placeholder material may be or include silicon nitride. The silicon nitride may be selectively removed and replaced with silicon which may serve as the conducting slabs of the VNAND structure in some embodiments. The slabs may be etched back up and down the slit trench to electrically separate them from one another. Overetching some and underetching other silicon layers may be minimized or avoided by etching the silicon of the VNAND structure more evenly with the methods presented herein. The yields and performance of VNAND devices may be improved using the present technologies. Although the remainder of this example will discuss silicon and silicon oxide, any other known materials used in these two layers may be substituted for one or more of the layers. Some or all of these operations may be performed in chambers or system tools as previously described, or may be performed in different chambers on the same system tool, which may include the chamber in which the operations of method 400 are performed. The patterned substrate is transferred into a substrate processing region in (optional) operation 410.

The method 400 may include flowing a fluorine-containing precursor into the substrate processing region of a semiconductor processing chamber at operation 415. An exemplary chamber may be chamber 200 previously described, which may include one or both of the RPS unit 201 or first plasma region 215. All regions which the fluorine-containing precursor pass through to reach the substrate processing region may be plasma-free and the substrate processing region may be plasma-free as well during operation 415 and also while selectively etching silicon evenly across the vertical distribution of levels in operation 420. The fluorine-containing precursor may interact with the patterned substrate in the processing region, which may include a trench formed through stacked layers of material, and which may include alternating layers of silicon and silicon oxide, for example, although other exposed dielectric materials may be used or present on the patterned substrate as well. The patterned substrate may have exposed portions of silicon (e.g. amorphous silicon or crystalline silicon), silicon oxide, and/or silicon nitride.

The fluorine-containing precursor may then laterally etch the layers of silicon during operation 420. The absence of plasma enables the etch process to proceed isotropically which makes the lateral etch of silicon possible. The lateral etching may be performed through a slit trench or may alternatively be used to remove or trim back features in a memory hole. The lateral etching may occur from sidewalls within the trench along an exposed portion of each layer of silicon. In some embodiments, the lateral etching may be selectively performed on the silicon layers, and may substantially maintain the intervening layers of silicon oxide or other dielectric material. Method 400 may laterally etch the silicon less than 12 nm from the sidewalls of the slit trench in exemplary operations before the lateral etching operation ends, while in other embodiments a greater amount of etching is performed. Regardless of the feature etched, less than 12 nm, less than 11 nm, less than 10 nm, less than 9 nm, less than 8 nm, less than 7 nm, less than 6 nm, less than 5 nm, less than 4 nm, less than 3 nm, less than 2 nm, or less than 1 nm of silicon may be removed in embodiments. The patterned substrate may be transferred out of the substrate processing region in optional operation 425.

Precursors used in the method may include a fluorine-containing precursor. An exemplary fluorine-containing precursor may be nitrogen trifluoride (NF₃), which may be flowed into the plasma-free substrate processing region, without passing through any plasma along the way. Other sources of fluorine may be used in conjunction with or as replacements for the nitrogen trifluoride. In general, a fluorine-containing precursor may be flowed into the remote plasma region and the fluorine-containing precursor may include at least one precursor selected from the group of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluoride, hydrogen fluoride, xenon difluoride, and various other fluorine-containing precursors used or useful in semiconductor processing. The precursors may also include any number of carrier gases, which may include nitrogen, helium, argon, or other noble, inert, or useful precursors. The carrier gases may be used to dilute the precursors, which may further reduce etching rates to allow adequate diffusion through the trench.

The V-profile may be unavoidable with conventional dry technologies because of the high aspect ratios of trenches or memory holes in which the lateral etching may be performed. The diameter or width of exemplary trenches may be a few tens of nanometers or less, while the height of the trenches may be on the order or a few microns or more. This may produce aspect ratios or height to width ratios of greater than 20:1, greater than 50:1, greater than 75:1, greater than 100:1, or even greater. Accordingly, in embodiments over 25 layers, over 50 layers, over 75 layers, or over one hundred layers of alternating silicon material and dielectric material may be formed and processed within each trench.

The etching may be performed for a period of time. In some embodiments the etching may be performed for greater than or about 30 seconds, greater than or about 1 minute, greater than or about 2 minutes, greater than or about 3 minutes, greater than or about 4 minutes, greater than or about 5 minutes, greater than or about 6 minutes, greater than or about 7 minutes, greater than or about 8 minutes, greater than or about 9 minutes, greater than or about 10 minutes, or more.

Process conditions may also impact the operations performed in method 400 as well as other etching methods according to the present technology. Each of the operations 415 and/or 420 of method 400 may be performed at a variety of substrate temperatures. For example, the substrate temperature during the etching operation 420 may be below 650° C., may be below 600° C., may be below 550° C., may be below 500° C., may be below 450° C., may be below 400° C., may be below 350° C., may be below 300° C., may be below 250° C., or may be below 200° C. in embodiments. The substrate temperature may affect the etching process itself, and higher temperature may produce higher etch rates due to the surface catalyzed mechanism of the precursors and materials presented herein. The substrate temperature during the etching operation 420 may be above 150° C., above 200° C., above 250° C., above 300° C., above 350° C., above 400° C., above 450° C., above 500° C., above 550° C., or above 600° C. according to embodiments. Upper temperature limits may be combined with lower temperature limits to form additional embodiments. In a preferred embodiment, the substrate temperature during the etching operation 420 may be between 350° C. and 500° C. Some fluorine-containing precursors may be undesirably dissociated in the gas phase if the fluorine-containing precursor comes in contact with surfaces which are above a threshold. Thus, no surfaces exposed within the substrate processing region may be above 450° C., above 500° C., above 550° C., above 600° C. or above 650° C. according to embodiments.

The partial pressure of the fluorine-containing precursor within the chamber may also affect the operations performed. The partial pressure of the fluorine-containing precursor may be the same as the total pressure in the absence of inert gases or carrier gases in embodiments. The partial pressure (or the total pressure) within the substrate processing region may be maintained above 1 Torr, above 5 Torr, above 10 Torr, above 20 Torr or above 50 Torr during etching operations according to embodiments. The partial pressure (or the total pressure) within the substrate processing chamber may be less than 2,000 Torr, less than 1,500 Torr, less than 1,000 Torr, less than 750 Torr, less than 500 Torr, or less than 350 Torr in embodiments, during any of the etching operations described herein. The upper limits and lower limits may be combined to form additional embodiments. Etch rate uniformity across substrates and within constrained geometries (e.g. slit trenches or memory holes) may be relatively unaffected by the partial pressure (or the total pressure) within the substrate processing region of the substrate processing chamber in embodiments. The substrate processing region partial pressure (or the total pressure) does affect the etch rate of exposed silicon portions of the patterned substrate and lower partial pressure (or the total pressure) embodiments (e.g. between 1 Torr and 350 Torr) may be selected if a slight recess is desired rather than a complete removal of a feature.

Benefits of the etching processes described herein may relate to the nature of the surface resident reactions of the fluorine-containing precursor with silicon and polysilicon surfaces (in the next example). The nature of the etching reactions may allow a more uniform, substantially uniform, or essentially uniform etch to be performed at each silicon region exposed within a slit trench or memory hole. In embodiments, a silicon region at or near the top of the trench or memory hole, such as within 2 layers from the top, within 4 layers, within 6 layers, within 8 layers, within 10 layers, or more, may have an amount of material etched measured from the sidewall that is similar to a silicon layer or region at or near the bottom of the trench of memory hole, such as within 2 layers from the bottom, within 4 layers, within 6 layers, within 8 layers, within 10 layers, or more.

The two layers being compared may be separated by at least 1 layer, at least 5 layers, at least 11 layers, at least 21 layers, at least 51 layers or more depending on the overall number of stacked layers within the structure through which the trench or memory hole has been etched. The lateral etch of the two layers being compared may differ by less than or about 30%, in terms of the upper layer being etched no more than 30% more than the lower layer. Additionally, the present technology may perform a lateral etch of the two layers so a difference between the amount of silicon etched between the two layers is less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, less than 1%, or zero difference in which case both regions of silicon are etched to an equal depth or distance from a sidewall of the slit trench or memory hole. Similarly, the amount of silicon maintained at each layer within the trench may be substantially similar to layers at any other location within the structure, and the amount of material remaining may differ between any two layers by less than 5 nm, and may differ by less than 4 nm, less than 3 nm, less than 2 nm, less than 1.5 nm, less than 1 nm, less than 0.5 nm, or less.

FIG. 5 shows exemplary operations in a method 500 according to embodiments of the present technology. Method 500 may include some or all of the operations of method 400 explained above, and may include any of the components or conditions discussed there. Method 500 may differ from method 400 by having polysilicon slabs instead of, the more general, silicon slabs. For example, method 500 may include forming a VNAND structure which has already had polysilicon slabs formed in an alternating pattern with silicon oxide at operation 505. The substrate may then be transferred into a substrate processing region in (optional) operation 510.

Method 500 may include flowing a fluorine-containing precursor into the substrate processing region of a semiconductor processing chamber at operation 515. The fluorine-containing precursor may be flowed into a remote plasma region and then into the substrate processing region, in which case the remote plasma region and the substrate processing region are plasma-free as discussed above. Alternatively, the fluorine-containing precursor may flow more directly into the substrate processing region, in which case the substrate processing region is plasma-free. All regions through which the fluorine-containing precursor the fluorine-containing precursor and any carrier gases pass are maintained plasma-free as defined herein during operation 520. The substrate processing region is devoid of gases other than the fluorine-containing precursor and inert gases according to embodiments.

The substrate may include a trench, such as a memory hole, formed through stacked layers including alternating polysilicon slabs and silicon oxide slabs. At operation 525, the polysilicon slabs may be etched. The reaction between the fluorine-containing precursor and the polysilicon slabs proceeds as a surface catalyzed reaction, according to embodiments, which may facilitate uniform etching of the polysilicon slabs laterally through the structure. The polysilicon etching may be performed at any of the conditions previously described within the context of etching silicon, and may produce similar results as described above, albeit at a lower etch rate. Analogously to the previous example, etch operation 525 may produce substantially uniform etching on the layers of polysilicon from the top of the trench to the bottom of the trench, also called top to bottom loading. This may allow a layer of polysilicon at an upper region of the trench and a layer of polysilicon at a lower region of the trench to differ in lateral etch amounts by less than about 20% or by any of the differences and/or depths as previously discussed. The uniformity may occur, in part, due to the conditions in which the operations are performed.

Turning to FIGS. 6A-6B are shown cross-sectional views of structure 600 being processed according to embodiments of the present technology. As illustrated in FIG. 6A substrate 605 may have a plurality of stacked layers overlying the substrate. The substrate may be silicon, silicon germanium, or other substrate materials. The layers may include alternating layers including dielectric material 610 and polysilicon 620 a. Polysilicon 620 a may be or include material that will be trimmed back to ensure that all the slabs are electrically isolated from one another. Although illustrated with only 7 layers of material, exemplary structures may include any of the numbers of layers previously discussed. Trenches 630, which may be slit trenches or memory holes and may be defined through the stacked structure to the level of substrate 605. Trenches 630 may be defined by sidewalls 632 that may be composed of the alternating layers of dielectric material 610 and polysilicon 620 a.

In FIG. 6B may be illustrated a structure after methods according to the present technology have been performed, such as discussed with respect to FIGS. 4-5 above. A portion of each exposed surface of polysilicon 620 a may be removed to form polysilicon layers 620 b. Following recession, polysilicon layers 620 b may be partially recessed from the sidewalls 632 of the trench 630 by less than 8 nm, less than 7 nm, less than 6 nm, less than 5 nm, less than 4 nm, less than 3 nm, less than 2 nm, or less than 1 nm in embodiments. The amounts etched previously as described previously in the context of polysilicon will not be repeated here for the sake of brevity. All dimensions, process traits and process parameters described herein apply to all other examples described herein regardless of material except when noted otherwise.

“Top” and “Up” will be used herein to describe portions/directions perpendicularly distal from the substrate plane and further away from the center of mass of the substrate in the perpendicular direction. “Vertical” will be used to describe items aligned in the “Up” direction towards the “Top”. “Lateral” is used to describe items or operations progressing in the “Horizontal” direction. Other similar terms may be used whose meanings will now be clear. A memory hole is oriented vertically and may be circular as viewed from above. A slit trench is also oriented vertically and may have a length longer than its width and generally the length is much longer than the width. The term “trench” is used generally throughout with no implication that the etched geometry has a large horizontal aspect ratio. Viewed from above the surface, trenches may appear circular, oval, polygonal, rectangular, or a variety of other shapes. The term “trench” encompasses both holes and long trenches.

Also in the methods described herein, the fluorine-containing precursor may react with exposed portions of silicon on a patterned substrate (under the conditions provided herein) to evenly, isotropically and selectively remove semiconductors (e.g. silicon) faster than dielectrics. The semiconductor may comprise or consist of silicon according to embodiments. The fluorine-containing precursor may react more readily with the silicon than with dielectrics as a consequence of the higher mobility of electrons within the silicon. The isotropic silicon etch may result in an etch selectivity (Si:SiO) which is greater than 20:1, greater than 30:1, greater than 50:1, greater than 75:1, greater than 100:1, greater than 125:1, or greater than 150:1 in embodiments. The etch technologies described herein may also result in an etch selectivity (Si:SiN) which is greater than 20:1, greater than 30:1, greater than 50:1, greater than 75:1, greater than 100:1, greater than 125:1, or greater than 150:1 according to embodiments. The etch selectivities, precursors, process parameters and process characteristics described herein may be applied to all disclosed embodiments and are not limited to the one particular embodiment in which the property is presented.

In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the above description should not be taken as limiting the scope of the technology. Additionally, methods or processes may be described as sequential or in steps, but it is to be understood that the operations may be performed concurrently, or in different orders than listed.

Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Any narrower range between any stated values or unstated intervening values in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the technology, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly dictates otherwise. Thus, for example, reference to “a precursor” includes a plurality of such precursors, and reference to “the layer” includes reference to one or more layers and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise(s)”, “comprising”, “contain(s)”, “containing”, “include(s)”, and “including”, when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or operations, but they do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups. 

1. An etching method comprising: flowing a fluorine-containing precursor into a substrate processing region of a semiconductor processing chamber, wherein a substrate is positioned within the substrate processing region and the substrate comprises silicon and a dielectric, wherein the silicon and the dielectric are exposed on sidewalls of a trench formed in stacked alternating layers of the silicon and the dielectric, and wherein the substrate processing region is maintained plasma-free while flowing the fluorine-containing precursor; and laterally removing silicon from the sidewalls of the trench at a greater removal rate than the dielectric.
 2. The method of claim 1, wherein the dielectric is one of silicon oxide or silicon nitride.
 3. The method of claim 1, wherein the lateral removal of silicon removes silicon with a horizontal etch progression.
 4. The method of claim 1, wherein the lateral removal of silicon removes silicon at an etch rate more than twenty times faster than the dielectric.
 5. The method of claim 1, wherein the lateral removal of silicon is performed at a substrate temperature of less than 500° C.
 6. The method of claim 1, wherein the lateral removal of silicon is performed at a partial pressure of fluorine-containing precursor which is more than 1 Torr.
 7. The method of claim 1, wherein the stacked alternating layers comprise at least 50 layers of alternating layers of the silicon and the dielectric.
 8. The method of claim 1, wherein the trench is characterized by an aspect ratio of greater than or about 50:1.
 9. The method of claim 1, wherein a layer of the silicon at an upper region of the trench and a layer of silicon at a lower region of the trench differ in lateral etch amounts by less than about 2 nm.
 10. The method of claim 1, wherein the fluorine-containing precursor is one of atomic fluorine, diatomic fluorine, nitrogen trifluoride, carbon tetrafluoride, hydrogen fluoride, or xenon difluoride.
 11. An etching method comprising: flowing a fluorine-containing precursor into a substrate processing region of a semiconductor processing chamber, wherein a substrate is positioned within the substrate processing region and the substrate comprises metal and dielectric, wherein the metal and the dielectric are exposed on sidewalls of a trench formed in stacked alternating layers of the metal and the dielectric, and wherein the substrate processing region is maintained plasma-free while flowing the fluorine-containing precursor; and laterally etching the metal from the sidewalls of the trench at a greater removal rate than the dielectric.
 12. The method of claim 11, wherein the metal is one of titanium or titanium nitride.
 13. The method of claim 11, wherein the lateral removal of metal removes metal with a horizontal etch progression.
 14. The method of claim 11, wherein the lateral removal of metal removes metal at an etch rate more than eight times faster than dielectric.
 15. The method of claim 11, wherein the lateral removal of metal is performed at a temperature of less than 500° C.
 16. The method of claim 11, wherein the lateral removal of metal is performed at a partial pressure of fluorine-containing precursor within the substrate processing region which is more than 1 Torr.
 17. The method of claim 11, wherein the trench is characterized by an aspect ratio of greater than or about 50:1.
 18. The method of claim 11, wherein the stacked alternating layers comprise at least 50 layers of alternating layers of the metal and the dielectric.
 19. The method of claim 11, wherein a layer of the metal at an upper region of the trench and a layer of silicon at a lower region of the trench differ in lateral etch amounts by less than about 2 nm. 